US20200079061A1 - Recyclable package with fitment - Google Patents

Recyclable package with fitment Download PDF

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Publication number
US20200079061A1
US20200079061A1 US16/562,610 US201916562610A US2020079061A1 US 20200079061 A1 US20200079061 A1 US 20200079061A1 US 201916562610 A US201916562610 A US 201916562610A US 2020079061 A1 US2020079061 A1 US 2020079061A1
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United States
Prior art keywords
polyethylene
density
fitment
minutes
melt index
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/562,610
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English (en)
Inventor
Robert Clare
Amin Mirzadeh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nova Chemicals International SA
Original Assignee
Nova Chemicals International SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nova Chemicals International SA filed Critical Nova Chemicals International SA
Priority to US16/562,610 priority Critical patent/US20200079061A1/en
Assigned to NOVA CHEMICALS (INTERNATIONAL) S.A. reassignment NOVA CHEMICALS (INTERNATIONAL) S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIRZADEH, AMIN, CLARE, ROBERT
Publication of US20200079061A1 publication Critical patent/US20200079061A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]

Definitions

  • a flexible package with an integral fitment is made from 90 to 100% polyethylene by weight, or for example from 95 to 100% by weight, allowing the package to be recycled.
  • the present disclosure provides a flexible package formed from
  • the present disclosure provides a flexible package formed from
  • the present disclosure provides a flexible package formed from
  • the present disclosure provides a flexible package formed from
  • each of the polyethylenes used to prepare the core of multilayer films has a melt index, I 2 , of from 0.5 to 10, or from 5 to 10, or from 0.5 to 5, and a density of from 0.91 to 0.94 g/cc, or 0.91 to 0.92 g/cc, or 0.92 to 0.94 g/cc with the further proviso that the polymeric material used to prepare said flexible package is at least 90% by weight polyethylene, or 95%, or 97%, or 100%.
  • the disclosure provides a process to prepare the flexible packages described above by heat sealing the multilayer film to the fitment.
  • the FIGURE illustrates the fitment used in the examples.
  • the packages of this disclosure include two components, namely a multilayer polyethylene film (described in Part A, below), and a fitment that is made from a linear low density polyethylene (described in Part B, below).
  • the multilayer polyethylene film used to prepare the packages of this disclosure include the following characteristics:
  • the fitment is made from a linear low density polyethylene having a dilution index, Yd, of greater than 0 (or for example from greater than 0 to about 7).
  • the polyethylene of the sealant layer is characterized by having a dilution index, Yd, of greater than 0 (or for example from greater than 0 to about 7).
  • both of the fitment and the sealant layer are made from a linear low density polyethylene that has a dilution index, Yd, of from 0 to about 7 (such polyethylene can be made in a dual reactor process).
  • the multilayer film is a laminated film (Part A.1, below). In another embodiment, the multilayer film is prepared by a coextrusion process (Part A.2, below). Details of the construction of the fitment are discussed in Part B, “Fitment,” below.
  • Suitable types of polyethylene to prepare the film include:
  • HDPE High Density Polyethylene
  • MDPE Medium Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • a sealant polyethylene a polyethylene material that is suitable for the preparation of a heat formed seal, for example a polyethylene selected from 1) a polyethylene copolymer having a density of from about 0.88 to 0.92 g/cc (“VLDPE”) and 2) a high pressure low density polyethylene (LD)—a polyethylene homopolymer prepared with a free radical initiator in a high pressure process, having a density of from about 0.91 to about 0.93 g/cc.
  • VLDPE polyethylene copolymer having a density of from about 0.88 to 0.92 g/cc (“VLDPE”) and 2) a high pressure low density polyethylene (LD)—a polyethylene homopolymer prepared with a free radical initiator in a high pressure process, having a density of from about 0.91 to about 0.93 g/cc.
  • the sealant polyethylene may also have a melt index, I 2 , of from 0.3 to 5, or for example 0.3 to 3 g/10 minutes.
  • the laminated structure is prepared using two distinct webs that are laminated together.
  • each web contains at least one layer of HDPE.
  • the HDPE layers provide rigidity/stiffness to the SUP.
  • These HDPE layers are separated by at least one layer of lower density polyethylene (such as LLDPE) and this lower density polyethylene provides impact and puncture resistance.
  • LLDPE lower density polyethylene
  • the overall rigidity and torsional strength of the SUP is improved in comparison to a structure that contains an equivalent amount/thickness of HDPE in a single layer—in a manner that might be referred to as an “I beam” effect (by analogy to the steel I beams that are in wide sue for the construction of buildings).
  • the optical properties are improved by adding a nucleating agent to the HDPE.
  • the optical properties are improved through the use of Machine Direction Orientation (MDO) of the outer/print web.
  • MDO Machine Direction Orientation
  • a skin layer of the web that has been subjected to MDO becomes a skin layer of the laminated film structure.
  • the optical properties are improved by the use of MDO on a web that contains a layer of nucleated HDPE.
  • the laminated structure is prepared with two webs, each of which contain at least one layer of HDPE. At least one HDPE layer in the first web is separated from at least one HDPE layer in the second web by a layer of lower density polyethylene, thereby optimizing the rigidity of the SUP for a given amount of HDPE.
  • the two webs are laminated together.
  • the laminated structure is printed at the interface between the two webs—i.e., either on the interior surface of the first web or on the exterior surface of the second web.
  • a layer of HDPE is used as a skin in the exterior web.
  • the first (exterior) web forms the outer wall of the laminated structure.
  • the laminated structure is printed on the interface between the first web and the second (interior) web.
  • the exterior web may be desirable for the exterior web to have low haze values.
  • a high “gloss” may be desirable as many consumers perceive a high gloss finish as being an indication of high quality.
  • the exterior web is subjected to Machine Direction Orientation (MDO) in an amount that is sufficient to improve the modulus (stiffness) and optical properties of the web.
  • MDO Machine Direction Orientation
  • the use of a thick monolayer HDPE film to form the exterior web could provide a structure with adequate stiffness.
  • a thick layer of HDPE may suffer from poor optical properties. This could be resolved by printing the exterior (skin) side of the outer web to form an opaque SUP.
  • this design may not be very abuse resistant as the printing can be easily scuffed and damaged during transportation and handling of the SUP.
  • these problems are mitigated by providing a coextruded multilayer film for the exterior web in which at least one skin layer (“layer A.1”) is prepared from HDPE and at least one layer (“layer A.2”) is prepared from a lower density polyethylene (such as LLDPE, LD or VLDPE).
  • layer A.1 skin layer
  • layer A.2 layer
  • LLDPE low density polyethylene
  • the HDPE is further characterized by having a melt index, I 2 , of from 0.1 to 10 (or for example from 0.3 to 3) grams/10 minutes.
  • the LLDPE is further characterized by having a melt index, I 2 , of from 0.1 to 5 (or for example from 0.3 to 3) grams/10 minutes.
  • the LLDPE is further characterized by being prepared using a single site catalyst (such as a metallocene catalyst) and having a molecular weight distribution, Mw/Mn (i.e., weight average molecular weight divided by number average molecular weight) of from about 2 to about 4.
  • a single site catalyst such as a metallocene catalyst
  • Mw/Mn molecular weight distribution
  • This type of LLDPE is typically referred to as sLLDPE (where “s” refers to the single site catalyst).
  • the very low density polyethylene is an ethylene copolymer having a density of from about 0.88 to 0.91 g/cc and a melt index, I 2 , of from about 0.5 to 10 g/cc. All of the materials described above are well known and commercially available.
  • the LLDPE used in web A is blended with a minor amount (from 0.2 to 10 weight %) of an LD polyethylene having a melt index, I 2 , of from 0.2 to 5, or for example from 0.2 to 0.8.
  • a minor amount from 0.2 to 10 weight % of an LD polyethylene having a melt index, I 2 , of from 0.2 to 5, or for example from 0.2 to 0.8.
  • an LD resin having a melt index of from about 0.2 to 0.8 grams/10 minutes has been observed to be effective for this purpose (and persons skilled in the art commonly refer to this type of LD resin as a “fractional melt LD”).
  • the LLDPE used in web A is blended with a minor amount (from 0.2 to 10 weight %) of an HDPE resin and a nucleating agent.
  • nucleating agent is meant to convey its conventional meaning to those skilled in the art of preparing nucleated polyolefin compositions, namely an additive that changes the crystallization behavior of a polymer as the polymer melt is cooled.
  • nucleating agents which are commercially available and in widespread use as polypropylene additives are the dibenzylidene sorbital esters (such as the products sold under the trademark MilladTM 3988 by Milliken Chemical and IrgaclearTM 287 by BASF Chemicals).
  • the nucleating agents should be well dispersed in the polyethylene.
  • the amount of nucleating agent used is comparatively small—from 200 to 10,000 parts by million per weight (based on the weight of the polyethylene) so it will be appreciated by those skilled in the art that some care should be taken to ensure that the nucleating agent is well dispersed.
  • the nucleating agent in finely divided form (less than 50 microns, or for example less than 10 microns) to the polyethylene to facilitate mixing.
  • nucleating agents which may be suitable for use include the cyclic organic structures disclosed in U.S. Pat. No. 5,981,636 (and salts thereof, such as disodium bicyclo [2.2.1] heptene dicarboxylate); the saturated versions of the structures disclosed in U.S. Pat. No. 5,981,636 (as disclosed in U.S. Pat. No. 6,465,551; Zhao et al., to Milliken); the salts of certain cyclic dicarboxylic acids having a hexahydrophtalic acid structure (or “HHPA” structure) as disclosed in U.S. Pat. No.
  • phosphate esters such as those disclosed in U.S. Pat. No. 5,342,868 and those sold under the trade names NA-11 and NA-21 by Asahi Denka Kogyo and metal salts of glycerol (for example zinc glycerolate).
  • the calcium salt of 1,2-cyclohexanedicarboxylic acid, calcium salt typically provides good results for the nucleation of HDPE.
  • the nucleating agents described above might be described as “organic” (in the sense that they contain carbon and hydrogen atoms) and to distinguish them from inorganic additives such as talc and zinc oxide. Talc and zinc oxide are commonly added to polyethylene (to provide anti-blocking and acid scavenging, respectively) and they do provide some limited nucleation functionality.
  • organic nucleating agents described above may be better (but more expensive) nucleating agents than inorganic nucleating agents.
  • the amount of organic nucleating agent is from 200 to 2000 parts per million (based on the total weight of the polyethylene in the layer that contains the nucleating agent).
  • these LLDPE/HDPE/nucleating agent blends have also been found to provide superior optical properties and higher modulus (higher stiffness) than 100% LLDPE.
  • the outer web is a three layer, coextruded film of the type A/B/A where A is an HDPE and B is a lower density polyethylene, for example the LLDPE compositions described above (including the LLDPE compositions that are blends with LD and LLDPE compositions that are blends with HD and a nucleating agent). These films provide good rigidity.
  • the outer web is a multilayer, coextruded film that includes at least one skin layer of HDPE and at least one layer of a lower density polyethylene such as MDPE or LLDPE.
  • the structure is subjected to Machine Direction Orientation (or MDO).
  • the MDO web is prepared from a multilayer film in which at least one of the layers is prepared from an HDPE composition and at least one of the layers is prepared from a polyethylene composition having a lower density than the HDPE composition.
  • MDO Machine Direction Orientation
  • the “precursor” film i.e., the film as it exists prior to the MDO process
  • the “precursor” film may be formed in any conventional film molding process. Two film molding processes that are in wide commercial use (and are suitable for preparing the precursor film) are the blown film process and the cast film process.
  • the precursor film is stretched (or, alternatively stated, strained) in the MDO process.
  • the stretching is predominantly in one direction, namely, the “machine direction” from the initial film molding process (i.e. as opposed to the transverse direction.
  • the thickness of the film decreases with stretching.
  • a precursor film that has an initial thickness of 10 mils and a final thickness after stretching of 1 mil is described as having a “stretch ratio” or “draw down” ratio of 10:1 and a precursor film that has an initial thickness of 10 ml and a final thickness of 2 ml having a “stretch” or “draw down” ratio of 2:1.
  • the precursor film may be heated during the MDO process.
  • the temperature is typically higher than the glass transition temperature of the polyethylene and lower than the melting temperature and more specifically, is typically from about 70 to about 120.degree. C. for a polyethylene film. Heating rollers may be used to provide this heat.
  • a typical MDO process utilizes a series of rollers that operate at different speeds to apply a stretching force on a film.
  • two or more rollers may cooperate together to apply a comparison force (or “nip”) on the film.
  • the stretched film is generally overheated (i.e. maintained at an elevated temperature—typically from about 90 to 125.degree. C.) to allow the stretched film to relax.
  • Inner Web (or “Sealant Web”)
  • the inner web forms the inside of a package that is prepared from the laminated structure.
  • the inner web is a coextruded film that includes at least three layers, namely B.1) a first layer (or interface skin layer) that is prepared from at least one polyethylene selected from LLDPE and MDPE; B.2) a core layer including an HDPE composition; and B.3) a sealant layer (or interior skin layer) that is prepared from a sealant polyethylene.
  • One skin layer of the inner web is prepared from a polyethylene composition having a lower density than HDPE so as to provide a layer having enhanced impact and tear strength properties in comparison to the layers prepared from HDPE.
  • this layer is made predominantly from an LLDPE, (including sLLDPE) having a melt index of from 0.3 to 3 grams per 10 minutes.
  • the layer may also be prepared using a major amount of LLDPE (or sLLDPE) and a minor amount of LD (for example a fractional melt LD, as described above) or the LLDPE+HDPE+nucleating agent blend as described above.
  • this skin layer may be prepared with MDPE (or a blend of MDPE with a minor amount of another polyethylene, such as the blends with LD; and the blends with HDPE and nucleating agent described above).
  • this skin layer is printed. Accordingly, it is within the scope of this disclosure to incorporate any of the well-known film modifications that facilitate the printing process.
  • the skin layer may be subjected to a corona treatment to improve ink adhesion.
  • the skin layer may contain an opacifying agent (such as talc, titanium oxide or zinc oxide) to improve the appearance of the printed surface.
  • the inner web includes at least one core layer that is prepared from an HDPE composition.
  • HDPE is a common item of commerce. Most commercially available HDPE is prepared from a catalyst that contains at least one metal (for example chromium or a group IV transition metal—Ti, Zr or Hf).
  • metal for example chromium or a group IV transition metal—Ti, Zr or Hf.
  • HDPE that is made from a Cr catalyst typically contains some long chain branching (LCB).
  • HDPE that is made from a group IV metal generally contains less LCB than HDPE made from a Cr catalyst.
  • the term HDPE refers to a polyethylene (or polyethylene blend composition, as required by context) having a density of from about 0.95 to 0.97 grams per cubic centimeter (g/cc).
  • the melt index (“I 2 ”) of the HDPE is from about 0.2 to 10 grams per 10 minutes.
  • the HDPE is provided as a blend composition including two HDPEs having melt indices that are separated by at least a decade. Further details of this HDPE blend composition follow.
  • Blend component a) of the polyethylene composition used in this embodiment includes an HDPE with a comparatively high melt index.
  • melt index is meant to refer to the value obtained by ASTM D 1238 (when conducted at 190° C., using a 2.16 kg weight). This term is also referenced to herein as “I 2 ” (expressed in grams of polyethylene which flow during the 10 minute testing period, or “gram/10 minutes”).
  • melt index, I 2 is in general inversely proportional to molecular weight.
  • blend component a) has a comparatively high melt index (or, alternatively stated, a comparatively low molecular weight) in comparison to blend component b).
  • the absolute value of I 2 for blend component a) in these blends is generally greater than 5 grams/10 minutes.
  • the “relative value” of I 2 for blend component a) is more important and it should generally be at least 10 times higher than the I 2 value for blend component b) (which I 2 value for blend component b) is referred to herein as I 2 ′).
  • I 2 ′ the I 2 value of blend component a) is preferably at least 10 grams/10 minutes.
  • blend component a) may be further characterized by: i) having a density of from 0.95 to 0.97 g/cc; and ii) being present in an amount of from 5 to 60 weight % of the total HDPE blend composition (with blend component b) forming the balance of the total composition) with amounts of from 10 to 40 weight %, for example from 20 to 40 weight %. It is permissible to use more than one high density polyethylene to form blend component a).
  • the molecular weight distribution (which is determined by dividing the weight average molecular weight (Mw) by number average molecular weight (Mn) where Mw and Mn are determined by gel permeation chromatography, according to ASTM D 6474-99) of component a) may be for example from 2 to 20, or for example from 2 to 4, or 4 to 10 or 10 to 20. While not wishing to be bound by theory, it is believed that a low Mw/Mn value (from 2 to 4) for component a) may improve the crystallization rate and overall barrier performance of blown films and web structures.
  • Blend component b) is also a high density polyethylene which has a density of from 0.95 to 0.97 g/cc (or for example from 0.955 to 0.968 g/cc).
  • the melt index of blend component b) is also determined by ASTM D 1238 at 190° C. using a 2.16 kg load.
  • the melt index value for blend component b) (referred to herein as I 2 ′) is lower than that of blend component a), indicating that blend component b) has a comparatively higher molecular weight.
  • the absolute value of I 2 ′ is, for example, from 0.1 to 2 grams/10 minutes.
  • Mw/Mn The molecular weight distribution (Mw/Mn) of component b) is not critical to the success of this disclosure, though a Mw/Mn of from 2 to 4 is an example of a useful Mw/Mn for component b).
  • the ratio of the melt index of component b) divided by the melt index of component a) is for example greater than 10/1.
  • Blend component b) may also contain more than one HDPE resin.
  • the overall high density blend composition is formed by blending together blend component a) with blend component b).
  • this overall HDPE composition has a melt index (ASTM D 1238, measured at 190° C. with a 2.16 kg load) of from 0.5 to 10 grams/10 minutes (or for example from 0.8 to 8 grams/10 minutes).
  • the blends may be made by any blending process, such as: 1) physical blending of particulate resin; 2) co-feed of different HDPE resins to a common extruder; 3) melt mixing (in any conventional polymer mixing apparatus); 4) solution blending; or, 5) a polymerization process which employs 2 or more reactors.
  • a suitable HDPE blend composition may be prepared by melt blending the following two blend components in an extruder: from 10 to 30 weight % of component a): where component a) is an HDPE resin having a melt index, I 2 , of from 15 to 30 grams/10 minutes and a density of from 0.95 to 0.97 g/cc with, from 90 to 70 weight % of component b): where component b) is an HDPE resin having a melt index, I 2 , of from 0.8 to 2 grams/10 minutes and a density of from 0.95 to 0.97 g/cc.
  • HDPE resin which is suitable for component a) is sold under the trademark SCLAIRTM 79F, which is an HDPE resin that is prepared by the homopolymerization of ethylene with a conventional Ziegler Natta catalyst. It has a typical melt index of 18 grams/10 minutes and a typical density of 0.963 g/cc and a typical molecular weight distribution of about 2.7.
  • SCLAIRTM 79F is an HDPE resin that is prepared by the homopolymerization of ethylene with a conventional Ziegler Natta catalyst. It has a typical melt index of 18 grams/10 minutes and a typical density of 0.963 g/cc and a typical molecular weight distribution of about 2.7.
  • the HDPE blend composition is prepared by a solution polymerization process using two reactors that operate under different polymerization conditions. This provides a uniform, in situ blend of the HDPE blend components.
  • the HDPE composition is prepared using only ethylene homopolymers. This type of composition is suitable if it is desired to optimize (maximize) the barrier properties of the structure.
  • the HDPE composition may be prepared using copolymers as this will enable some improvement in the physical properties, for example, impact resistance.
  • a minor amount (less than 30 weight %) of a lower density polyethylene may be blended into the HDPE composition (as again, this can enable some improvement in impact resistance).
  • the HDPE blend composition described above is combined with an organic nucleating agent (as previously described) in an amount of from about 300 to 3000 parts per million by weight, based on the weight of the HDPE blend composition.
  • organic nucleating agent as previously described
  • the use of (previously described) calcium salt of 1,2-cyclohexane dicarboxylic acid, calcium salt (CAS 491589-22-1) is suitable.
  • the presence of the nucleating agent has been observed to improve the modulus of the HDPE layer (in comparison to a non-nucleated layer of equivalent thickness).
  • nucleated HDPE blend composition of the type described above provides a “barrier” to oxygen and water transmission.
  • the performance of this barrier layer is suitable for many goods.
  • improved “barrier” performance can be achieved through the use of certain “barrier” polymers such as ethylene-vinyl-alcohol (EVOH); ionomers and polyamides.
  • EVOH ethylene-vinyl-alcohol
  • ionomers ionomers
  • polyamides polyamides.
  • the use of large amounts of such non-polyethylene barrier resins can make it very difficult to recycle films/structures/SUP that are made with the combination of polyethylene and non-polyethylene materials. However, it is still possible to recycle such structures if low amounts (less than 10 weight %, or for example less than 5 weight %) of the non-polyethylene materials.
  • non-polyethylene barrier resins may require the use of a “tie layer” to allow adhesion between the non-polyethylene barrier layer and the remaining layers of polyethylene.
  • the interior web has two exterior layers, or “skin” layers, namely the interface skin layer (layer B.1, above) and the interior skin layer (also referred to herein as the sealant layer.
  • the sealant layer is prepared from a “sealant” polyethylene—i.e., a type of polyethylene that readily melts and forms seals when subjected to sealing conditions.
  • a “sealant” polyethylene i.e., a type of polyethylene that readily melts and forms seals when subjected to sealing conditions.
  • two types of polyethylene may be preferred for use as sealants, namely: polyethylene copolymers having a density of from about 0.88 to 0.92 g/cc; and LD polyethylene (as previously described).
  • the use of lower density polyethylene copolymers is preferred.
  • the cost of these lower density polyethylene's increases as the density decreases, so the “optimum” polyethylene sealant resin will typically be the highest density polyethylene that provides a satisfactory seal strength.
  • a polyethylene having a density of from about 0.900 to 0.912 g/cc will provide satisfactory results for many applications.
  • sealant polyethylenes include ethylene-vinyl acetate (EVA) and “ionomers” (e.g., copolymers of ethylene and an acidic comonomer, with the resulting acid comonomer being neutralized by, for example, sodium, zinc or lithium; ionomers are commercially available under the trademark SURLYN).
  • EVA ethylene-vinyl acetate
  • ionomers e.g., copolymers of ethylene and an acidic comonomer, with the resulting acid comonomer being neutralized by, for example, sodium, zinc or lithium; ionomers are commercially available under the trademark SURLYN).
  • EVA and/or ionomers are less preferred because they can cause difficulties when the SUP is recycled (however, as previously noted, some recycling facilities will accept a SUP that contains up to 10% of EVA or ionomer and recycle the SUP as if it were constructed from 100% polyethylene).
  • the laminated structure may be printed at the interface between the two webs.
  • Suitable processes include the well-known flexographic printing and roto gravure printing techniques, which typically use nitro cellulose or water based inks.
  • One step in the fabrication of the laminated structure requires the lamination of the first web to the second web.
  • a liquid glue which may be solvent based, solventless, or water based
  • a hot melt glue which may be solvent based, solventless, or water based
  • thermal bonding there are many commercially available techniques for the lamination step, including the use of a liquid glue (which may be solvent based, solventless, or water based); a hot melt glue, and thermal bonding.
  • the inner web B has a total thickness that is about twice that of the outer web A.
  • the outer web A may have a thickness of from about 1 to about 1.4 mils and the inner web may have a thickness of from about 2 to about 3 mils.
  • the outer web includes an exterior skin layer made from HDPE (having a thickness of, for example, about 0.8 mils) and a layer of LLDPE having a thickness of, for example, about 0.4 mils.
  • the inner layer may be an A/B/C structure where layer A is made from LLDPE (having a thickness of, for example, about 0.4 mils; layer B is nucleated HDPE (having a thickness of, for example, about 1.5 mils) and layer C is sealant resin (such as VLDPE) having a thickness of, for example, about 0.3 mils.
  • the above described thickness may be easily modified to change the physical properties of the SUP.
  • the thickness of the HDPE layers may be increased (if it is desired to produce a stiffer SUP) or the thickness of the LLDPE layer(s) may be increased to improve impact resistance.
  • the total thickness of the laminated structure i.e., outer web and inner web
  • the total thickness of the laminated structure is about 3 to about 4 mils in one embodiment.
  • the multilayer film that is used to prepare the package is prepared by a coextrusion process.
  • the laminated film structure described in Part A.1 above and the coextruded film structures generally use the same (or very similar) materials of construction, with the main difference between the two types of film structures being that the “coextruded” structures do not require a lamination step—instead, all of the film layers are coextruded.
  • the “laminated” films can provide enhanced print quality and improved scuff resistance.
  • the coextruded films do not require the “lamination” step and hence may be less expensive to prepare than laminated films.
  • the total thickness of the coextruded film structure can be essentially the same as the total thickness of the laminated structure (and the thickness of the layers in both structures can be essentially the same).
  • “essentially the same thicknesses” are those films with a measured thickness within about 5% or less of each other, or for example within about 1% or less, or for example 0.5% or less.
  • flexible packages having integral fitments tend to have size ranges from a few tens of millimeters at the small end to about 30 liters at the large end.
  • the fitment size generally is proportional to the size of the package—i.e. smaller fitments are used with smaller packages and larger fitments are used with larger packages.
  • the size of the fitment opening (which allows the contents of the package to be removed from it) will also generally be proportional to the package size—although it is also well known to use larger openings for packages that contain solids and/or viscous liquids or slurries (in comparison to smaller diameter fitments that may be used with non viscous liquids such as soft drinks).
  • the fitment may contain a valve to control flow of a liquid from the pouch. More commonly, the fitment will have a threaded connection that cooperates with a threaded cap or closure.
  • the fitment may be designed to improve the sealability of the fitment to the film and/or the strength of the fitment.
  • Common examples of such fitments include “shoulders” around the fitment opening—and “ribs” along the depth of the fitment.
  • One type of fitment is referred to as a “canoe” because a top view of the fitment resembles the shape of a canoe—the use of this type of fitment is illustrated in the examples.
  • a “ribbed canoe” fitment has two or more ribs that run the outside length of the canoe—with the ribs being at different depths from the top of the canoe.
  • the fitments of this disclosure are made from LLDPE having a density of from 0.88 to 0.93 g/cc—or for example from 0.91 to 0.93 g/cc.
  • the melt index, I 2 , of the LLDPE used to prepare the fitment may be from 0.2 to about 150, or from 0.2 to 10, or from 0.2 to 50, or from 0.2 to 100, or from 50 to 100, or from 100 to 150.
  • the I 2 of the LLDPE used to prepare the fitment may be higher than the I 2 of the polyethylenes used to prepare the film.
  • the LLDPE used to prepare the fitment may have a melt index, I 2 , of from 0.2 to 50 (or for example from 0.2 to 20) g/10 minutes.
  • Such LLDPE may be prepared by the copolymerization of ethylene with at least one alpha olefin comonomer (or for example butene-1; hexene-1 and/or octene-1).
  • the LLDPE may have a “homogenous” branch distribution (i.e. having an SCBDI of from 70 to 100) or a “heterogeneous” branch distribution (i.e. having an SCBDI of less than 70).
  • the LLDPE has a Dilution Index, Yd, of greater than 0 (or for example greater than 0 to 7).
  • Yd Dilution Index
  • Such LLDPE may be prepared in a dual reactor polymerization process. The method to determine/measure Dilution Index, Yd, is described in U.S. Pat. Nos. 9,512,282 and 10,035,906.
  • welding heat sealing
  • Common/conventional techniques are generally suitable.
  • ultrasonic and laser sealing technique can be used.
  • LLDPE linear low density polyethylene
  • This type of LLDPE is a well-known item of commerce.
  • Typical commercially available, LLDPE is a copolymer of ethylene and one alpha olefin comonomer chosen from butene-1, hexene-1 and octene-1 (and it is also known to use mixtures of more than one of these comonomers to prepare LLDPE).
  • the LLDPE has a melt index, “I 2 ”, (as determined by ASTM D1923 at 190° C. with a 2.16 kg load) of from 0.2 to 20 grams per 10 minutes, or from 0.2 to 5, or from 5 to 10, or from 10-20, or from 7 to 15.
  • I 2 melt index
  • the LLDPE may be prepared in any type of polymerization process (such as a gas phase; slurry; or solution process) using any suitable type of catalyst, including “homogenous” catalysts (also referred to as “single site” catalysts) or heterogenous catalysts.
  • Metallocene catalysts are well known “homogeneous” catalysts.
  • Ziegler Natta catalyst are well known heterogeneous catalysts.
  • the resulting LLDPE may have a “homogeneous” comonomer incorporation (as indicated by having a Short Chain Branching Distribution Index, or SCBDI, of greater than 70%) or a “heterogeneous” comonomer distribution. It is also known to prepare LLDPE in a multi-reactor process in which a homogeneous catalyst is used in one reactor and a heterogeneous catalyst is used in another—and such LLDPE is suitable for use in this disclosure.
  • Dilution Index is based on rheological measurements.
  • blends of ethylene polymers may exhibit a hierarchical structure in the melt phase.
  • the ethylene polymer components may be, or may not be, homogeneous down to the molecular level depending on polymer miscibility and the physical history of the blend.
  • Such hierarchical physical structure in the melt is expected to have a strong impact on flow and hence on processing and converting; as well as the end-use properties of manufactured articles.
  • the nature of this hierarchical physical structure between ethylene polymers can be characterized by Yd (“Dilution Index”). Yd values greater than 0, or for example from greater than 0 to 7, are used in an embodiment.
  • the branching distribution in ethylene copolymers may be defined using the so called short chain branching distribution index (SCBDI).
  • SCBDI short chain branching distribution index
  • Polyethylene copolymers that are prepared with a metallocene catalyst generally have a narrow branching distribution (which corresponds to a high SCBDI value).
  • SCBDI is defined as the weight % of the polymer that has a comonomer content with 50% of the median comonomer content of the polymer.
  • SCBDI is determined according to the method described in U.S. Pat. No. 5,089,321 (Chum et al.).
  • SCBDI of from about 70 to about 100 may be used to define/describe a “narrow branching distribution” in an ethylene copolymer.
  • a multilayer polyethylene film (as described above) was used in this example.
  • Multilayer Film (or Recyclable Film)
  • the multilayer film used in the examples (also referred to as “recyclable” film for convenience) is a laminated film that was prepared in accordance with known/published techniques.
  • the film has an outer web that is laminated to a sealant web.
  • sealant web The compositions of the webs are described below.
  • the sealant web was also made by a three layer coextrusion—with the thickness of the sealant web being 2.35 mils (and the layers having thickness values of 0.4; 1.5 and 0.45 mils, respectively).
  • the laminated film was made by laminating the above two webs together using a conventional adhesive. The following types of polyethylene were used (in the amounts and places indicated above).
  • PE1 polymer homopolymer
  • melt index I 2 1 g/10 minutes
  • density 0.958 g/cc (sold as SCLAIR 19C by NOVA Chemicals)
  • PE2 ethylene-hexene copolymer
  • melt index I 2 0.8 g/10 minutes
  • density 0.954 g/cc (sold as NOVAPOL 534 by NOVA Chemicals);
  • PE3 nucleated blend of ethylene homopolymers
  • melt index I 2 1.2 g/10 minutes
  • density 0.967 g/cc (sold as SURPASS HPs 167 by NOVA Chemicals);
  • the FIGURE illustrates the fitment that was used in these examples.
  • the fitment may be described as being “canoe” shaped, to employ a term that is commonly used by those skilled in the art.
  • the length of the fitment is 35 mm; the width of the fitment (at the widest part of the “canoe”) is 14.15 mm; the thickness is 9.2 mm and the circular hole in the fitment has a diameter of 9 mm.
  • LLDPEs Fitments made from LLDPE were prepared.
  • the LLDPEs used have the following characteristics:
  • sLLDPE1 melt index 4 g/10 minutes; density 0.912 g/cc. (Ex-VPS412 sLLDPE Resin)
  • sLLDPE2 melt index 4.5 g/10 minutes; density 0.917 g/cc. (FPS417 sLLDPE Resin)
  • sLLDPE3 melt index 0.85 g/10 minutes; density 0.913 g/cc. (VPsK914 sLLDPE Resin)
  • sLLDPE4 melt index 0.85 g/10 minutes; density 0.921 g/cc.
  • LLPDE1 is sold under the name NOVAPOLTM 2024; HDPE2 is sold under the name SCLAIRTM 2710 and both are commercially available from NOVA Chemicals Corporation.
  • Table 1 provides a summary of sealing times and temperatures that are required to produce good seals between the film and the LLDPE fitment. For clarity: Table 1 shows that a good seal strength was obtained using a minimum sealing time of 5 seconds at 120° C. or for a minimum sealing time of 2 seconds at 140° C. or for a minimum sealing time of 0.75 second at 160 1° C. at 3 bars of pressure. However, higher temperatures (above 160° C.) caused excessive softening of the film structure in less than 1 second, leading to unacceptable packages (noted with the “*” symbol).
  • Acceptable seal strength cannot be achieved between the film and the HDPE fitment at 120° C. or at 140° C. and less than 8 seconds sealing time or 160° C. at 4 seconds. Again, high temperature and/or high sealing time leads to excessive softening of film structure causing the package failure.
  • sLLDPE1 produced proper seal using a sealing time of 2 seconds at 120° C., or in less than 1 second at 140° C.
  • inventive examples described above illustrate that good seals may be produced between the recyclable multilayer film and a fitment made from LLDPE. This is a highly desirable result because it allows the manufacture of a “recyclable” flexible package with a fitment (and, as noted, prior attempts to head weld the recyclable film of this disclosure to a fitment made from HDPE in a commercial packaging machine were not successful).
  • the example illustrates a set of experiments that were completed in order to develop a surface response model that describes the seal strength.
  • Conventional Design of Experiments (DOE) software was used to choose the experiments and sealing conditions.
  • a flat plaque the flexural modulus specimen
  • heat seals were formed between the recyclable film used in the experiments and flat plaques that were made from the above-mentioned LLDPEs (instead of fitments made from the same LLDPEs).
  • the use of a flat plaque is convenient because it simplifies the sealing machinery and because it facilitates the testing of the strength of the seal.
  • the sealed samples were then tested for seal strength using a Universal Testing Machine.
  • Table 3 illustrates data that describe the seals that were formed between the recyclable film and LLDPE1 (NOVAPOLTM 2024).
  • Table 4 illustrates data that describe the seals that were formed between the recyclable film and LLDPE2 (SCLAIRTM 2114).
  • Table 5 illustrates data that describe the seals that were formed between the recyclable film and sLLDPE1 (Ex-VPS412 sLLDPE Resin).
  • Table 6 illustrates data that describe the seals that were formed between the recyclable film and sLLDPE2 (FPS417 sLLDPE Resin).
  • Table 7 illustrates data that describe the seals that were formed between the recyclable film and sLLDPE3 (VPsK914 sLLDPE Resin).
  • Table 8 illustrates data that describe the seals that were formed between the recyclable film and LLDPE4 (SPsK919 sLLDPE Resin).
  • Table 9 illustrates data that describe the seals that were formed between the recyclable film and HDPE1 (SCLAIRTM 2714).
  • Table 10 illustrates data that describe the seals that were formed between the recyclable film and HDPE1 (SCLAIRTM 2710).

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
US16/562,610 2018-09-10 2019-09-06 Recyclable package with fitment Abandoned US20200079061A1 (en)

Priority Applications (1)

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US16/562,610 US20200079061A1 (en) 2018-09-10 2019-09-06 Recyclable package with fitment

Applications Claiming Priority (2)

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US201862729024P 2018-09-10 2018-09-10
US16/562,610 US20200079061A1 (en) 2018-09-10 2019-09-06 Recyclable package with fitment

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US20200079061A1 true US20200079061A1 (en) 2020-03-12

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US (1) US20200079061A1 (fr)
EP (1) EP3849792B1 (fr)
JP (1) JP7312246B2 (fr)
KR (1) KR102786407B1 (fr)
CN (1) CN112996656A (fr)
AR (1) AR116388A1 (fr)
BR (1) BR112021004467B1 (fr)
CA (1) CA3053597A1 (fr)
ES (1) ES3033932T3 (fr)
MX (1) MX2021002176A (fr)
WO (1) WO2020053708A1 (fr)

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WO2023198612A1 (fr) * 2022-04-11 2023-10-19 Borealis Ag Film
WO2024068314A1 (fr) * 2022-09-30 2024-04-04 Totalenergies Onetech Film asymétrique, orienté dans le sens machine, de polyéthylène formé par extrusion à plat, pourvu de propriétés d'étanchéité et stratifié comprenant un tel film
EP4249246A4 (fr) * 2020-12-23 2024-05-15 Toppan Inc. Stratifié et sac d'emballage
US20240157687A1 (en) * 2021-06-10 2024-05-16 Sk Innovation Co., Ltd. Polyethylene Film Having Multi-Layer Structure and Packaging Material Produced Using the Same

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US20240157687A1 (en) * 2021-06-10 2024-05-16 Sk Innovation Co., Ltd. Polyethylene Film Having Multi-Layer Structure and Packaging Material Produced Using the Same
US12454120B2 (en) * 2021-06-10 2025-10-28 Sk Innovation Co., Ltd. Polyethylene film having multi-layer structure and packaging material produced using the same
WO2023198612A1 (fr) * 2022-04-11 2023-10-19 Borealis Ag Film
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WO2024068314A1 (fr) * 2022-09-30 2024-04-04 Totalenergies Onetech Film asymétrique, orienté dans le sens machine, de polyéthylène formé par extrusion à plat, pourvu de propriétés d'étanchéité et stratifié comprenant un tel film

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KR20210057731A (ko) 2021-05-21
AR116388A1 (es) 2021-05-05
JP7312246B2 (ja) 2023-07-20
BR112021004467A2 (pt) 2021-05-25
EP3849792B1 (fr) 2025-06-04
BR112021004467B1 (pt) 2023-12-05
ES3033932T3 (en) 2025-08-11
MX2021002176A (es) 2021-04-28
CN112996656A (zh) 2021-06-18
KR102786407B1 (ko) 2025-03-24
CA3053597A1 (fr) 2020-03-10
EP3849792C0 (fr) 2025-06-04
EP3849792A1 (fr) 2021-07-21
WO2020053708A1 (fr) 2020-03-19

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